The electrochemical reduction of an aryl diazonium tetrafluoroborate salt, dissolved in acetonitrile, at a carbon electrode surface allowed the grafting of aryl groups with the formation of a carbon-carbon bond. Groups such as 4-carboxyphenyl, 4-nitrophenyl, 4-diethylaniline (DEA), and 4-bromophenyl were grafted at a glassy carbon electrode surface. The stability of these grafted groups, present at the glassy carbon electrode surface, was studied at various electrode potentials in aqueous media. In appropriate experimental conditions, the as-grafted groups severely inhibit the cyclic voltammetry response of selected redox probes. Thus, the reappearance and/or increase of an electrochemical response, after polarization, was taken as an indication that a modification of the grafted layer occurred. Our results demonstrated that polarization at very positive (ca. 1.8 V) and negative (ca. -2 V) potentials is needed to observe an electrochemical response. Electrochemical impedance and X-ray photoelectron spectroscopies were also used to investigate the stability of the grafted layers. The impedance data usually tracks fairly well the cyclic voltammetry results, although the former appears to be more sensitive to changes that are occurring upon polarization of the modified electrode. Interestingly, the XPS data indicate clearly that the grafted layer is not always completely removed at the extreme positive and negative potentials investigated. A mechanism was proposed to explain the transformation occurring during polarization of the modified electrode and involves desorption of the substituted aryl groups during the concomitant hydrogen, oxygen, or chlorine evolution and finally leaving close to a covalently bonded monolayer of the grafted species at the electrode surface.

Brightly and uniformly colored passive layers on Ti are formed by application of ac polarization in aqueous NH4BF4. A wide spectrum of well-defined colors is accomplished by varying the ac voltage. The passive films are stable in the ambient and in aqueous chloride, perchlorate, and sulfate solutions. Optical microscopy and scanning electron microscopy analyses indicate that the passive layers are compact and do not show fractures or cracks. An X-ray photoelectron spectroscopy (XPS) characterization of the colored passive layers demonstrates that their surface-chemical composition depends on the ac polarization voltage. The main constituents of the passive layers are Ti z+ , O 2-, and F -(z varies from 4 to 2 depending on the film's depth). Fluoride in the film originates from decomposition of NH4BF4, and it accumulates at the inner metal/passive-film interface. XPS depth profiling shows that the higher the ac voltage applied, the thicker the passive film formed. Electrochemical properties of the colored Ti passive layers are determined by recording polarization curves in the -0.8 to 3.2 V range as well as Tafel plots in the hydrogen evolution reaction (HER) region in 1.0 M aqueous H2SO4. The polarization curves show that the corrosion potential of the colored passive layers shifts toward less-negative potentials indicating that they are more stable than Ti under the same conditions. The passive region for the colored layers resembles that for Ti. The Tafel plots for the HER demonstrate that the passive layers have higher activity toward the HER than Ti. The Tafel relations reveal new features that can be associated with the partial breakdown/decomposition of the passive layers, H absorption, and the onset of Ti hydride formation.

Two-component substituted aryl groups are simultaneously grafted onto the surface of a glassy carbon electrode by electrochemical reduction of a binary mixture of two aryl diazonium salts in acetonitrile. The electrochemical deposition is achieved potentiostatically and two different mixtures with four different ratios of diazonium salts are used. The binary mixtures comprise: 1) 4-nitrophenyl diazonium and 4-bromophenyl diazonium cations and 2) 4-bromophenyl diazonium and N,N-diethylaniline diazonium cations. The chemical composition of the two component films is determined by cyclic voltammetry in an electrolyte inert for electroactive groups such as nitrophenyl and bromophenyl. X-ray photoelectron spectroscopy is also used to evaluate the surface concentration of each grafted substituted phenyl group. The surface concentration of the substituted phenyl group for which the corresponding diazonium cation is the most easily reduced is higher than its concentration in the mixture of the deposition solution. The usefulness of binary films is also discussed.

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